EP1093449B1 - Ammoniumnitratkörper und verfahren zu ihrer herstellung - Google Patents

Ammoniumnitratkörper und verfahren zu ihrer herstellung Download PDF

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Publication number
EP1093449B1
EP1093449B1 EP99955261A EP99955261A EP1093449B1 EP 1093449 B1 EP1093449 B1 EP 1093449B1 EP 99955261 A EP99955261 A EP 99955261A EP 99955261 A EP99955261 A EP 99955261A EP 1093449 B1 EP1093449 B1 EP 1093449B1
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EP
European Patent Office
Prior art keywords
poly
weight
sulphonate
styrene
ammonium nitrate
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99955261A
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English (en)
French (fr)
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EP1093449A1 (de
Inventor
John Cooper
Michael Brues
Noel Hsu
Ronald O. Peddie
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Orica Explosives Technology Pty Ltd
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Individual
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/18—Nitrates of ammonium

Definitions

  • This invention relates to ammonium nitrate bodies produced by spraying a liquid mixture of ammonium nitrate and water that is highly concentrated in ammonium nitrate (herein "AN") in to an atmosphere where the AN rapidly crystallises and water is removed by evaporation.
  • the bodies may be prills (i.e. dense round particles resulting from crystallisation of free-falling droplets of mixture) or agglomerates (i.e. less dense associations of the component AN crystallites, irregular in shape and dimensions) or granules (i.e. generally round particles grown by spraying the mixture on to tumbling seed material such as small AN prill so that layers of AN crystals become encrusted on the seed material).
  • the invention is particularly concerned with ammonium nitrate bodies for use in explosives products, but is not restricted to such bodies.
  • the invention may also extend to such bodies for use in fertiliser products.
  • AN prill intended for use as oxidiser in explosives products is required to have a sufficient porosity to allow absorption of from 6 to 12% by weight of fuel oil and yet be a particulate free-flowing product which can be poured or augered into bore-holes.
  • This product is so-called ANFO.
  • Such a prill is also a very satisfactory material for blending with emulsion explosive .
  • the AN/water mixture should contain up to, at most, around 97.5% by weight of AN, the preferred range being 92-97.5%, more preferably 94-96% by weight AN.
  • the water content of the AN/water mixture also influences the density and friability of the AN prill.
  • AN prill which is produced from an AN/water mixture containing at least 98% by weight AN is hard, dense and of low porosity.
  • Other characteristics of an explosives grade AN prill that influence friability and stability towards atmospheric changes are the micro-crystalline structure and the residual moisture content of the prill. These characteristics are important also in other forms of AN bodies used as solid oxidiser in explosives products, e.g. pan-granulated AN particles, although they would not possess the hardness or low friability desired in an explosive grade AN prill.
  • the AN bodies intended for use as explosives' oxidant will preferably consist of AN. It is, however, known to substitute some of the AN by alkali- and/or alkaline metal nitrates in explosives' oxidisers, and references herein to AN should be construed as AN optionally with a proportion of the ammonium nitrate substituted by one or more such other nitrate oxidant. Thus, references to AN proportions in the feed mixtures may for practical purposes be read as proportions of total nitrate oxidant.
  • the present invention further provides a process for producing AN bodies by prilling, pan-granulation or other means of production of AN particles composed of aggregates of AN crystals in which an AN/water mixture as immediately hereinbefore described is sprayed with cooling to effect crystallisation of the AN followed by drying in a stream of gas, especially air, to remove substantially all free moisture, preferably to a residual water content of at most 0.1% water by weight in the dried product.
  • the process type is preferably prilling under conditions of acoustic frequency vibratory prilling such that substantially mono-sized prills are produced, with drying effected in one or a train of two or more rotary driers under co- or counter current drying gas, e.g. air, flow, and the process is preferably in accordance with the immediately preceding paragraphs.
  • the present invention also provides AN bodies, especially AN prills, produced by a process as described in either of the two immediately preceding paragraphs.
  • the invention also extends to the use of a synergistic combination of poly-styrene sulphonate and ammonium sulphate as crystal-habit modifier in the production of ammonium nitrate prill, especially explosive-grade ammonium nitrate prill.
  • the AN/water mixture preferably contains at most about 97.5%, more preferably 94-97%, even more preferably 95-97%, by weight of AN. However, the AN/water mixture may contain more AN if the AN bodies are to be used in fertiliser products.
  • the concentration of poly-styrene sulphonate is at least 0.02% by weight of the mixture.
  • concentration of poly-styrene sulphonate is at most about 0.06% by weight, more preferably at most about 0.05% by weight, even more preferably of most about 0.04% by weight.
  • the mixture further includes a quantity of ammonium sulphate which is greater than the quantity of poly-styrene sulphonate present, preferably at a concentration in the mixture of, say, 0.06 to 0.15% by weight for example about 0,07 to about 0.13% by weight, more preferably 0.08 to 0.13% by weight.
  • the poly-styrene sulphonate may be considered to be present as its ammonium salt, given the preponderance of ammonium ions present in the mixture and the normal practice of pH adjustment to a value of around 5.5 by ammonia addition.
  • Poly-styrene sulphonate exists as a range of molecules, not merely because as a polymer there will be a range of chain lengths determined by the polymerisation process and any fractionation, but also because the degree of sulphonation of polymer chains can vary widely. Thus, at one end of the spectrum of possible molecules is poly (vinyl benzene sulphonate) and descending from that best characterised species are a range of sulphonated poly-styrenes.
  • sulphonated poly-styrenes with more than 90% degree of sulphonation from a range of poly-styrenes with number average molecular weights from 40,000 to 200,000; all were effective additives. Higher molecular weight materials are more viscous and this can make production and handling more difficult. Low molecular weight material has been produced by styrene polymerisation followed immediately by sulphonation without any intermediate separation or purification stages. These materials had molecular weights centred around 10,000 to 20,000 and again were found to be effective.
  • reaction product may be neutralised with ammonia and the result then is a mixture of the sulphonated polymer and ammonium sulphate which may be used in the process of the invention to produce the ammonium nitrate bodies.
  • the ratio of polymer to ammonium sulphate by weight may be in the range of from about 1:5 to about 1:10, and this range is also very suitable for mixtures made by mixing separately obtained components.
  • poly-styrene sulphonate alone in minor amounts as a crystal-habit modifier (say, at a concentration by weight in the AN/water mixture fed to the spray head of 0.06 %) is that it permits production of AN bodies having a lower standing water content than is achievable under similar regimes of thermal/humidity gradient using ammonium sulphate or other known crystal-habit modifiers alone.
  • a residual water content of, at best, 0.1% by weight would typically be observed for product prill made using other crystal-habit modifiers
  • the use of poly-styrene sulphonate enables AN prill to be recovered with a water content as low as 0.05%, even 0.03% by weight.
  • Poly-styrene of desired molecular weight is dispersed as a fine powder in 98% strength sulphuric acid containing silver sulphate catalyst at a temperature in the range 98 to 120 degrees Celsius.
  • the powdered poly-styrene is added with intensive stirring to ensure dissolution. Reaction proceeds in the course of this addition and then subsequently for a sufficient period to achieve the desired or maximum degree of sulphonation.
  • Reactor product is neutralised with ammonia.
  • styrene is first polymerised by low temperature (15 to 20 degrees Celsius) cationic polymerisation in a mixture of 96% strength sulphuric acid (90 parts by weight) and phosphoric acid fortified with phosphorus pentoxide (10 parts by weight). A small amount of surfactant (dipropylene glycol diphosphoric acid) is included. After polymerisation has proceeded sufficiently, the temperature is raised to effect sulphonation as described above. The reactor product is neutralised with ammonia.
  • Example 3 Three equal weight samples of ammonium nitrate/water mixtures were prepared containing 90% by weight AN. To one sample (Sample 1) a quantity of poly (vinyl benzene sodium sulphonate) was added. Its concentration in the liquor was 0.06% by weight. To another sample (Sample 2) a mixture of 1 part by weight of the same sulphonate and 4 parts by weight of ammonium sulphate was added. The concentration of the sulphonate in the liquor was 0.02 % by weight. The third sample (Sample 3) was used as such, without any additive.
  • this example shows that drying rate is enhanced by the additives and that, if ammonium sulphate is present, the concentration of the poly-styrene sulphonate may be reduced substantially without loss of drying rate.
  • a pilot scale prilling plant was used to produce AN prill samples.
  • the plant was a reduced scale version of a commercial prilling plant.
  • the prilling column interior measured 0.6m x 9m through which ambient air was passed.
  • the solidified prills were directed to first and second rotary drum driers for moisture removal by co- or counter current air flows (0.7m/s).
  • the temperature in the first drier was in the range 50 to 70 degrees Celsius and the temperature in the second was 50 degrees Celsius.
  • the drums rotated at 8 rpm and were provided with several sample take-off points along their lengths so that the rate and extent of moisture removal could be monitored.
  • the prilling head was vibrated laterally at a selected acoustic frequency and the prills produced were substantially mono-sized at about 1.7mm diameter .
  • the feed AN liquor was either 94% or 96% AN strength.
  • Poly-styrene sulphonate and/or ammonium sulphate were included in the AN liquor.
  • the AN liquor feed rate was 60 kg/hr and drying times were ordinarily between 30 and 60 minutes.
  • Table 2 presents results from a sequence of runs.
  • the "% weight additive in feed” gives the proportion of poly-styrene sulphonate and/or ammonium sulphate in the feed, with the proportion of ammonium sulphate being determined by subtracting the "% weigh poly-SS”.
  • poly-SS stands for poly-styrene sulphonate; in runs 1-3 it was a poly(vinylbenzene sulphonate) of medium average molecular weight; in runs 4-7 it was the product of sulphonating a medium molecular weight poly-styrene by the method described above, followed by ammonia neutralisation; in run 11 it was the material of run 1 mixed with reagent grade ammonium sulphate.
  • Relative friability figures indicate a measure of fines production after submitting product prills to a particular attrition regime; it is the trend of the displayed values that is significant.
  • Runs 1 and 2 show the results obtained using poly-SS alone at a concentration of 0.06% by weight in the AN liquor; run 3 shows that reducing the amount of poly-SS to 0.02% by weight gave poor results the product was wet.
  • Run 4 in comparison to run 3, shows the benefit of a co-presence of ammonium sulphate at 0.13% by weight in the AN liquor.
  • Run 8 shows that ammonium sulphate alone at that level is ineffective.
  • Run 5 shows that at this scale of operation a low concentration of both additives was ineffective. However, as runs 6 and 7 show, increasing the ammonium sulphate concentration restored product quality. Run 9 shows the effect of a high concentration of ammonium sulphate alone. Runs 10 and 11 show results when a more aqueous AN feed liquor is used. In run 10 there was no additive; in run 11 the additive was a mixture very rich in ammonium sulphate and the product prill showed good oil absorbancy and good friability for a low density material.
  • results at commercial scale indicate a lower threshold for poly-styrene sulphonate of 0.01% by weight of the feed AN liquor and a lower threshold for ammonium sulphate of 0.04% by weight, but preferably it is present at a concentration of at least 0.06% by weight and more preferably up to 0.15% or higher.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Fertilizers (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (14)

  1. Verfahren zur Herstellung von Ammoniumnitrat-Körpern in Form von Teilchen, bei dem eine flüssige Ammoniumnitrat/Wasser-Mischung, die mindestens 92 Gew.-% Ammoniumnitrat, wobei gegebenenfalls ein Teil des Ammoniumnitrats durch ein Alkali- und/oder Erdalkalimetallnitrat ersetzt ist, und eine geringe Menge Polystyrolsulfonat-Modifizierungsmittel in Kristallform enthält, in Form von Tröpfchen in eine Atmosphäre versprüht wird, wobei die Abkühlung eine Kristallisation des Ammoniumnitrats bewirkt, und bei dem die kristallisierten Teilchen getrocknet werden, um die Feuchtigkeit zu entfernen, dadurch gekennzeichnet, dass die flüssige Mischung außerdem Ammoniumsulfat enthält, dass die Konzentration des Polystyrolsulfonats in der flüssigen Mischung mindestens 0,01 Gew.-% beträgt und die Konzentration des Ammoniumsulfats in der flüssigen Mischung größer ist als diejenige des Polystyrolsulfonats und mindestens 0,04 Gew.-% beträgt.
  2. Verfahren nach Anspruch 1, das ein Sprühkristallisations- bzw. Prilling-Verfahren ist.
  3. Verfahren nach Anspruch 1 oder 2, bei dem die flüssige Mischung höchstens etwa 97,5 Gew.-% Ammoniumnitrat enthält.
  4. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Polystyrolsulfonat-Konzentration mindestens 0,02 Gew.-% beträgt.
  5. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Polystyrolsulfonat-Konzentration höchstens etwa 0,06 Gew.-% beträgt.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Ammoniumsulfat-Konzentration in dem Bereich von etwa 0,06 bis etwa 0,15 Gew.-% liegt.
  7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Verhältnis von Polystyrolsulfonat zu Ammoniumsulfat in dem Bereich von etwa 1 : 5 bis etwa 1 : 10 liegt.
  8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Polystyrolsulfonat ein Poly(vinylbenzolsulfonat) ist.
  9. Verfahren nach einem der Ansprüche 1 bis 7, bei dem das Polystyrolsulfonat ein nachträglich sulfoniertes Polystyrol ist, dessen Sulfonierungsgrad, bezogen auf Poly(vinylbenzolsulfonat), mindestens 50 % beträgt.
  10. Verfahren nach Anspruch 9, bei dem das Polystyrolsulfonat hergestellt worden ist durch einen Sulfonierungsprozess, bei dem das Sulfonat in einem Schwefelsäure-Medium gebildet und die restliche Schwefelsäure mit Ammoniak neutralisiert wird, sodass das Sulfonat im Gemisch mit Ammoniumsulfat vorliegt, und diese Mischung zur Herstellung der Ammoniumnitratkörper verwendet wird.
  11. Verfahren nach Anspruch 10, bei dem das Polystyrol hergestellt wird durch Polymerisieren von Styrol und das Polystyrol dann sulfoniert wird, ohne es vorher zu isolieren.
  12. Ammoniumnitrat-Körper, insbesondere -Prills, die nach einem Verfahren nach einem der vorhergehenden Ansprüche hergestellt worden sind.
  13. Ammoniumnitrat-Körper nach Anspruch 12, die weniger als 0,1 Gew.-% Wasser enthalten und in der Lage sind, nicht weniger als 6 % ihres Gewichtes an Heiz- bzw. Dieselöl zu absorbieren, wobei sie noch ein gießbares teilchenförmiges Material bleiben.
  14. Verwendung einer synergistischen Kombination von Polystyrolsulfonat und Ammoniumsulfat-Modifizierungsmittel in Kristallform zur Herstellung von Ammoniumnitrat-Prills, insbesondere von Ammoniumnitrat-Prills von Sprengstoff-Qualität.
EP99955261A 1998-06-03 1999-06-02 Ammoniumnitratkörper und verfahren zu ihrer herstellung Expired - Lifetime EP1093449B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9811824.3A GB9811824D0 (en) 1998-06-03 1998-06-03 Modified ammonium nitrate
GB9811824 1998-06-03
PCT/GB1999/001752 WO1999062845A1 (en) 1998-06-03 1999-06-02 Ammonium nitrate bodies and a process for their production

Publications (2)

Publication Number Publication Date
EP1093449A1 EP1093449A1 (de) 2001-04-25
EP1093449B1 true EP1093449B1 (de) 2003-08-13

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EP99955261A Expired - Lifetime EP1093449B1 (de) 1998-06-03 1999-06-02 Ammoniumnitratkörper und verfahren zu ihrer herstellung

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US (1) US6572833B1 (de)
EP (1) EP1093449B1 (de)
CN (1) CN1144773C (de)
AP (1) AP2000002012A0 (de)
AU (1) AU750665B2 (de)
BR (1) BR9910930A (de)
CA (1) CA2333741C (de)
DE (1) DE69910393T2 (de)
GB (1) GB9811824D0 (de)
ID (1) ID27187A (de)
NO (1) NO20010515L (de)
OA (1) OA11560A (de)
WO (1) WO1999062845A1 (de)
ZA (1) ZA200007792B (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002232417B2 (en) * 2000-12-19 2006-09-21 The Lubrizol Corporation Aminosulfonate product-treated nitrogen-containing salt particles
CA2503819C (en) * 2004-04-08 2014-01-21 Nexco Inc. Method of producing ammonium nitrate crystals
CA2464278A1 (en) * 2004-04-08 2005-10-08 Christopher Preston Ammonium nitrate blasting agent and method of production
CN100358845C (zh) * 2006-02-27 2008-01-02 广东省四○一厂 高密度膨化硝铵炸药的制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8728564D0 (en) 1987-12-07 1988-01-13 Ici Plc Controlled break-up of liquid jets
GB2266724A (en) * 1992-05-04 1993-11-10 Ici Canada Hardened Porous Ammonium Nitrate
GB9209619D0 (en) 1992-05-05 1992-06-17 Ici Plc Granulated ammonium nitrate products
GB9209621D0 (en) 1992-05-05 1992-06-17 Ici Plc Improved prill process
FR2701942B1 (fr) 1993-02-24 1995-05-19 Prod Ind Cfpi Franc Additif interne et procédé pour la préparation de certaines formes cristallisées du nitrate d'ammonium et applications industrielles de celles-ci.
PL176297B1 (pl) * 1995-02-21 1999-05-31 Inst Przemyslu Organiczego Sposób otrzymywania porowatej saletry amonowej
FR2757842B1 (fr) * 1996-12-31 1999-11-19 Kaltenbach Thuring Sa Procede et installation pour la fabrication de nitrate d'ammoniaque poreux

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Publication number Publication date
AU750665B2 (en) 2002-07-25
NO20010515D0 (no) 2001-01-30
EP1093449A1 (de) 2001-04-25
GB9811824D0 (en) 1998-07-29
DE69910393T2 (de) 2004-08-05
CN1304391A (zh) 2001-07-18
WO1999062845A1 (en) 1999-12-09
AP2000002012A0 (en) 2000-12-31
AU4276299A (en) 1999-12-20
US6572833B1 (en) 2003-06-03
CN1144773C (zh) 2004-04-07
NO20010515L (no) 2001-01-30
CA2333741A1 (en) 1999-12-09
ZA200007792B (en) 2002-03-22
BR9910930A (pt) 2001-02-20
CA2333741C (en) 2008-03-25
OA11560A (en) 2004-05-26
ID27187A (id) 2001-03-08
DE69910393D1 (de) 2003-09-18

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